KR20140113706A - Process for production of hexamethylenediamine from 5-hydroxymethylfurfural - Google Patents

Abstract

A process for the conversion of a carbohydrate source to hexamethylenediamine (HMDA) and an intermediate useful for the production of hexamethylenediamine and other industrial chemicals is disclosed. The HMDA is produced by direct reduction of 1,6-hexanediol in the furfural substrate in the presence of a heterogeneous reduction catalyst comprising hydrogen and Pt, or by indirect reduction of the furfural substrate to 1,6-hexanediol, wherein 1,2,6-hexanetriol is produced by reduction of the furfural substrate in the presence of a catalyst comprising hydrogen and Pt, and 1,2,6-hexanetriol is then produced in the presence of a catalyst comprising Pt , 6-hexanediol, and each step precedes the production of HMDA by a known route, such as the amination of 1,6-hexanediol. Catalysts useful for the direct and indirect production of 1,6-hexanediol are also disclosed.

Description

PROCESS FOR PRODUCTION OF HEXAMETHYLENEDIAMINE FROM 5-HYDROXYMETHYLFURFURAL FROM 5-HYDROXYMETHYLFURURAL [0002]

Cross reference of related application

This application claims the benefit of U.S. Provisional Application No. 61 / 588,093, filed January 18, 2012, the content of which is incorporated herein by reference in its entirety.

Technical field

This disclosure relates generally to processes for the conversion of carbohydrate sources to hexamethylenediamine and hexamethylenediamine and other intermediates useful for the production of other industrial chemicals. This disclosure relates more particularly to a chemical catalytic process for the production of hexamethylenediamine from a furfural substrate derived from a carbohydrate source which is catalyzed by chemical catalyzed amination of the diol to produce a hexamethylenediamine, 6-hexanediol. ≪ / RTI > The present invention also relates to the production of 1,6-hexanediol from a furfural substrate wherein at least a portion of the furfural substrate is converted to 1,2,6-hexanetriol and then at least a portion of the hexanetriol is replaced by 1 , 6-hexanediol, followed by conversion of 1,6-hexanediol to hexamethylenediamine by, for example, chemical-catalyzed amination of the diol. This disclosure also relates to an improved process for the production of hexanediol from furfural substrates.

Hexamethylenediamine (HMDA) is a chemical intermediate primarily used in the production of nylon 6,6 through condensation with adipic acid. HMDA is also used in the production of monomers for polyurethanes. In addition, HMDA is used in the production of epoxy resins. Today, the annual production of HMDA exceeds 3 billion pounds (avoir).

Crude oil is currently the source of most essential and specialty organic chemicals. Most of these chemicals are used in the production of polymers and other materials. Preferred chemicals are, for example, styrene, bisphenol A, terephthalic acid, adipic acid, caprolactam, hexamethylenediamine, adiponitrile, caprolactone, acrylic acid, acrylonitrile, 1,6- Propanediol, and the like. Crude oil is first purified by steam cracking, typically with hydrocarbon intermediates such as ethylene, propylene, butadiene, benzene, and cyclohexane. These hydrocarbon intermediates are then typically subjected to one or more catalytic reactions by various processes to produce the desired chemical (s).

HMDA is still commercially produced from oils through a multi-step process among these chemicals. HMDA is typically produced from butadiene. Butadiene is typically produced from steam cracking of heavy feedstocks. Steam pyrolysis of these feedstocks prefer to produce butadiene, but also produce heavy olefins and aromatics. Thus, the butadiene from the pyrolysis step is typically extracted with a polar solvent and removed therefrom by distillation. The butadiene undergoes a hydrocyanation process in the presence of a nickel catalyst, whereby adiponitrile is produced. See, for example, US 6,331,651. Next, HMDA is produced by hydrogenation of adiponitrile, typically in the presence of a solid catalyst. For example, US 4,064,172 discloses a process for producing HMDA by hydrogenating adiponitrile in the presence of an iron oxide catalyst, and US 5,151,543, which discloses a process for the production of HMDA from at least one metal element selected from Groups 4, 5 and 6 of the Periodic Table of Elements Discloses that HMDA can be prepared by hydrogenating adiponitrile in the presence of a doped Raney nickel type catalyst) and more recently WO-A-93/16034 and WO-A-96/18603, ≪ / RTI > discloses a Raney nickel catalyst-based process for the production of HMDA from U.S. Pat. 2003/0144552 (which discloses the process of producing HMDA from adiponitrile in the presence of a specially conditioned Raney nickel catalyst).

It should be noted that the above-mentioned documents on the production of HMDA each recognize the need for improvement in the efficiency, selectivity and commercial competitiveness of this process. In fact, the need for an improved or alternative commercial process for the production of HMDA produces less amount of butadiene when pyrolyzed and, ultimately, increases the cost of HMDA production and increases the cost of chemicals The industry is deepening by the development.

For many years, he was interested in using bio-renewable materials as raw materials to replace or replenish crude oil. See, for example, Klass, Biomass for Renewable Energy, Fuels, and Chemicals, Academic Press, 1998, incorporated herein by reference.

In recent years, among other substances, HMDA and other chemicals used in the production of polymers such as nylon have been found to be bio-renewable resources, particularly those that can be produced from carbohydrate-containing materials that can be used as feedstocks for the production of glucose, Respectively. See, for example, US 2010/0317069, which discloses biological routes that are thought to be useful for producing caprolactam and HMDA among other chemicals.

So far, there has been no commercially viable process for the production of HMDA from carbohydrate containing raw materials. Out of the conventional oil-derived starting materials such as butadiene, due to the continued growth of the nylon and polyurethane market and the use of renewable raw materials instead of petroleum-derived raw materials among other materials at least partly derived from HMDA or its derivatives Despite the benefits that may be obtained, selective and commercially significant production of chemicals from polyhydroxyl-containing bio-renewable materials (e.g. glucose from starch, cellulose or sucrose) to important chemical intermediates such as HMDA The new industrial-scale method for a

1,6-Hexanediol (HDO) has been prepared from, for example, adipic acid, caprolactone and hydroxycaproic acid. See, for example, US 5,969,194. Recently, a process for the production of 1,6-hexanediol from furfural derived from glucose has been disclosed in WO2011 / 149339. The '339 application provides a general description of at least two-step catalytic processes for the production of HDO from 5-hydroxymethyl furfural (HMF), which is 2,5-bis (hydroxymethyl) tetrahydrofuran (BHMTHF, 2 , 5-tetrahydrofurandimethanol or THFDM), followed by hydrogenation of BHMTHF with 1,2,6-hexanetriol (HTO); And then the hydrogenation of 1,2,6-hexanetriol with 1,6-hexanediol. The process disclosed in the '339 application requires at least two different catalyst systems to produce 1,6-hexanediol from HMF. In addition, the reported yield of HDO from HMF is 4% (with direct HDO) to 22% (using a three step process: from HMF to THFDM, from THFDM to HTO and then from HTO to HDO). The low yield reported in the '339 application clearly demonstrates the need for the development of alternative, more efficient processes for the production of HDO.

Briefly, therefore, the present invention provides a method of treating cancer, comprising: converting a carbohydrate source to a furfural substrate; Reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6-hexanediol; And converting at least a portion of the 1,6-hexanediol into hexamethylenediamine. The present invention also relates to a process for preparing hexamethylenediamine from a carbohydrate source. The present invention also relates to a method for the treatment of cancer, comprising: converting a carbohydrate source to a furfural substrate; Reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce a reaction product comprising 1,2,6-hexanetriol; Converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol; And converting at least a portion of the 1,6-hexanediol into hexamethylenediamine. The present invention also relates to a process for preparing hexamethylenediamine from a carbohydrate source. In some embodiments, the heterogeneous reduction catalyst comprises Pt. In another embodiment, the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re. In another embodiment, the step of converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol is carried out in the presence of a hydrogenation catalyst comprising hydrogen and Pt. In another embodiment, the yield of 1,6-hexanediol is at least about 40%. In another embodiment, the yield of 1,6-hexanediol is at least about 50%. In another embodiment, the yield of 1,6-hexanediol is at least about 60%. In other embodiments, the reaction of the furfural substrate with hydrogen is performed at a temperature in the range of about 60 DEG C to about 200 DEG C and a hydrogen pressure in the range of about 200 psig to about 2000 psig. In another embodiment, the furfural substrate is 5-hydroxymethyl furfural. In another embodiment, the carbohydrate source is a mixture comprising glucose, fructose, or glucose and fructose. In another embodiment, the catalyst further comprises a support selected from the group consisting of zirconia, silica and zeolite. In another embodiment, the reaction of the furfural substrate with hydrogen is performed at a temperature in the range of about 100 ° C to about 180 ° C and a hydrogen pressure in the range of about 200 psig to about 2000 psig. In another embodiment, the hydrogenation catalyst comprises Pt and W supported on zirconia. The present invention also relates to hexamethylenediamine produced by the process of any of the above embodiments.

The present invention also relates to a method for the treatment of cancer, comprising: converting a carbohydrate source to a furfural substrate; Hexanediol from a carbohydrate source by reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol . The present invention also relates to a method for the treatment of cancer, comprising: converting a carbohydrate source to a furfural substrate; Reacting at least a portion of the furfural substrate with hydrogen in the presence of a Pt containing heterogeneous reduction catalyst to produce a reaction product comprising 1,2,6-hexanetriol; Hexanediol from a carbohydrate source by converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol. In some embodiments, the heterogeneous catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re. In another embodiment, the step of converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol is carried out in the presence of a hydrogenation catalyst comprising hydrogen and Pt. In another embodiment, the hydrogenation catalyst is a supported heterogeneous catalyst. In another embodiment, the yield of 1,6-hexanediol from the furfural substrate is at least 40%. In another embodiment, the yield of 1,6-hexanediol from the furfural substrate is at least 50%. In another embodiment, the yield of 1,6-hexanediol from the furfural substrate is at least 60%. In other embodiments, the reaction of the furfural substrate with hydrogen is performed at a temperature in the range of about 60 DEG C to about 200 DEG C and a hydrogen pressure in the range of about 200 psig to about 2000 psig. In another embodiment, the furfural substrate is 5-hydroxymethyl furfural. In another embodiment, the carbohydrate source is a mixture comprising glucose, fructose, or glucose and fructose. In another embodiment, the catalyst further comprises a support selected from the group consisting of zirconia, silica and zeolite. In another embodiment, the reaction of furfural substrate with hydrogen is performed at a temperature in the range of about 100 ° C to about 140 ° C and a hydrogen pressure in the range of about 200 psig to about 1000 psig. In another embodiment, the catalyst comprises Pt and W supported on zirconia. The present invention also relates to 1,6-hexanediol produced by the process of any of the above embodiments.

The present invention also relates to a process for the preparation of a furfural substrate comprising: (a) converting a carbohydrate source to a furfural substrate; (b) reacting hydrogen with at least a portion of the furfural substrate with a reaction product comprising 1,2,6-hexanetriol in the presence of a heterogeneous reduction catalyst comprising Pt; (c) reacting at least a portion of 1,2,6-hexanetriol with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol; And (d) converting hexamethylenediamine into hexamethylenediamine by converting at least a portion of the 1,6-hexanediol into a hexamethylenediamine, wherein steps b) and c) are carried out in a single reactor . The present invention also relates to a process for the preparation of a furfural substrate comprising: (a) converting a carbohydrate source to a furfural substrate; (b) reacting hydrogen with at least a portion of the furfural substrate with a reaction product comprising 1,2,6-hexanetriol in the presence of a heterogeneous reduction catalyst comprising Pt; And (c) reacting at least a portion of the 1,2,6-hexanetriol with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol from the carbohydrate source, Hexanediol, wherein steps b) and c) are carried out in a single reactor. In some embodiments, the heterogeneous reduction catalyst further comprises W. In another embodiment, steps b) and c) are performed at a temperature in the range of about 60 캜 to about 200 캜 and a hydrogen pressure in the range of about 200 psig to about 2000 psig. In another embodiment, the Pt containing catalyst of step b) and c) are different and the temperature and pressure at which steps b) and c) are carried out are substantially the same. In another embodiment, the temperature and pressure at which steps b) and c) are performed are different. In another embodiment, step b) is performed at a temperature in the range of about 100 캜 to about 140 캜 and a pressure in the range of about 200 psig to about 1000 psig, and step c) is performed at a temperature in the range of about 120 캜 to about 180 캜, At a pressure ranging from 200 psig to about 2000 psig. In another embodiment, the yield of 1,6-hexanediol from the furfural substrate is at least about 40%. In another embodiment, the yield of 1,6-hexanediol from the furfural substrate is at least about 50%. In another embodiment, the yield of 1,6-hexanediol from the furfural substrate is at least about 60%. In another embodiment, the carbohydrate source is a mixture comprising glucose, fructose, or glucose and fructose. In another embodiment, steps b) and c) are carried out in one reaction zone. In another embodiment, the catalyst comprises Pt and W supported on zirconia. The present invention also relates to hexamethylenediamine produced by the process of any of the above embodiments. The present invention also relates to 1,6-hexanediol produced by the process of any of the above embodiments.

The present invention also relates to a method for the treatment of cancer, comprising: converting a carbohydrate source to a furfural substrate; And reacting hydrogen with at least a portion of the furfural substrate in the presence of a heterogeneous reduction catalyst comprising Pt to produce a compound of formula II:

Where X ² and X ³ are each selected from the group of hydrogen and hydroxyl. In some embodiments, the catalyst further comprises W. In another embodiment, the catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re.

The following description provides exemplary methods, variables, and the like. It should be appreciated, however, that such description is not intended as a limitation on the scope of the invention.

According to the present invention, the Applicant has found that a process for the chemical catalytic conversion of furfural substrate to hexamethylenediamine, which may be derived from a carbohydrate source (e.g., glucose or fructose) And the product. In some embodiments, the process comprises converting the carbohydrate source to a furfural substrate; Reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6-hexanediol; And converting at least a portion of the 1,6-hexanediol into hexamethylenediamine. In another embodiment, the process comprises converting the carbohydrate source to a furfural substrate; Reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce a reaction product comprising 1,2,6-hexanetriol; Converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol; And converting at least a portion of the 1,6-hexanediol into hexamethylenediamine. In some embodiments, the process comprises converting the carbohydrate source to a furfural substrate; And reacting hydrogen with at least a portion of the furfural substrate in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol. In another embodiment, the process comprises converting the carbohydrate source to a furfural substrate; Reacting at least a portion of the furfural substrate with hydrogen in the presence of a Pt containing heterogeneous reduction catalyst to produce a reaction product comprising 1,2,6-hexanetriol; And converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol. In another embodiment, the process comprises: (a) converting a carbohydrate source to a furfural substrate; (b) reacting hydrogen with at least a portion of the furfural substrate with a reaction product comprising 1,2,6-hexanetriol in the presence of a heterogeneous reduction catalyst comprising Pt; (c) reacting at least a portion of 1,2,6-hexanetriol with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol; And (d) converting at least a portion of the 1,6-hexanediol into hexamethylenediamine, wherein steps b) and c) are carried out in a single reactor. In another embodiment, the process comprises: (a) converting a carbohydrate source to a furfural substrate; (b) reacting hydrogen with at least a portion of the furfural substrate with a reaction product comprising 1,2,6-hexanetriol in the presence of a heterogeneous reduction catalyst comprising Pt; And (c) reacting hydrogen with at least a portion of 1,2,6-hexanetriol in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol, wherein step b) And c) are carried out in a single reactor. In a preferred embodiment, the 1,6-hexanediol is converted to hexamethylenediamine by chemical catalytic amination.

In another aspect of the present invention, the hexamethylenediamine prepared according to the disclosed process can be prepared according to procedures known in the art, for example, using various other industrially important chemicals including monomers for nylon 6,6 and polyurethane And chemical precursors.

Vegetable biomass, agricultural waste, forest residues, sugar residues, plant-derived waste, municipal waste, waste paper, switchgrass, miscassus, carcass, as well as corn kernels (corn), beet and sugarcane All of the bio-renewable sources of supply, such as wildflowers, trees (hardwoods and softwoods), vegetables, and crop residues (eg, bergas and corn bushes) are rich in hexoses and are rich in 5- (hydroxymethyl) furfural Can be used to produce the same furfural derivatives. Hexose can be easily produced by hydrolysis from such carbohydrate sources. It is also generally known that biomass carbohydrates can be enzymatically converted to glucose, fructose and other sugars. Dehydration of fructose can easily produce furan derivatives such as 5- (hydroxymethyl) furfural. Acid hydrolysis of glucose is also known to produce 5- (hydroxymethyl) furfural. See, for example, U.S. Pat. 6,518,440. A variety of other methods have been developed to produce 5- (hydroxymethyl) furfural, see, for example, U.S. Pat. 4,533, 743 (Medeiros et al.); U.S. Pat. 4,912,237 (Zeitsch); U.S. Pat. 4,971,657 (Avignon et al.); U.S. Pat. No. 6,743,928 (Zeitsch); U.S. Pat. 2,750,394 (Peniston); U.S. Pat. 2,917,520 (Cope); U.S. Pat. 2,929,823 (Garber); U.S. Pat. 3,118,912 (Smith); U.S. Pat. 4,339, 387 (Fleche et al.); U.S. Pat. 4,590,283 (Gaset et al.); And U.S. Pat. 4,740,605 (Rapp). Among the foreign patent documents GB 591,858; GB 600,871; And GB 876,463, all of which have been published in English. FR 2,663,933; FR 2,664,273; FR 2,669,635; And CA 2,097,812, both of which are published in French. As such, a number of carbohydrate sources may be used to produce 5- (hydroxymethyl) furfural by various known techniques.

In some preferred embodiments, the carbohydrate source is glucose, and glucose is converted to fructose using methods known in the art, such as industrial processes to convert glucose to high-fructose corn syrup. As described above, several processes have been disclosed for the production of furfural substrates (e.g., 5- (hydroxymethyl) furfural) from, for example, glucose or other hexoses.

I. furfural substrate and its reduction

Applicants have discovered that a compound of formula II can be prepared by chemically catalyzing hydrogen with a furfural substrate of formula I in the presence of a heterogeneous catalyst comprising platinum (Pt) according to the following overall reaction:

Wherein each X ² and X ³ is independently hydrogen or hydroxyl. According to various embodiments of the present invention, X ² is hydrogen or hydroxyl and X ³ is preferably hydrogen.

In various embodiments, the reaction is conducted in the presence of a Pt-containing catalyst at a temperature (s) in the range of from about 60 ° C to about 200 ° C and at a pressure (s) in the range of from about 200 psig to about 2000 psig.

According to various embodiments of the present invention, the compound of formula Ha is prepared by reacting 5- (hydroxymethyl) furfural (HMF) with HMF and hydrogen in the presence of a catalyst comprising Pt to produce a reaction product comprising a compound of formula Ha , Wherein the overall reaction is as follows, wherein X < ² > is hydroxyl or hydrogen:

According to another embodiment of the present invention, 5- (hydroxymethyl) furfural is first converted into a first set of 5- (hydroxymethyl) furfural to convert at least a portion of 5- (hydroxymethyl) furfural into 1,2,6- Reacting with hydrogen in the presence of a catalyst comprising Pt in the reaction conditions and at least a portion of the 1,2,6-hexanetriol being subsequently reacted in the presence of a catalyst comprising Pt in a second set of reaction conditions, Hexanediol, and the overall reaction is as follows:

In certain embodiments of the present invention, a first reduction reaction to convert 5- (hydroxymethyl) furfural to a reaction product comprising 1,2,6-hexanetriol and a first reduction reaction to convert 1,2,6-hexanetriol A second reduction reaction to convert at least a portion of the triol to 1,6-hexanediol may be achieved in a single reaction zone wherein the reaction conditions are modified after a predetermined period of time to effect conversion of the triol to the diol.

In various other embodiments of the present invention, the first reduction reaction and the second reduction reaction are carried out in a limited zone of a single reactor, for example a fixed bed trickle reactor, wherein the first zone contains 1,2,6-hexanetriol Wherein the first reduction catalyst is operated in reaction conditions to produce a reaction product to convert at least a portion of the triol into a 1,6-hexanediol, . In such embodiments, the catalysts may be the same or different, and the first set of reaction conditions and the second set of reaction conditions may be the same or different. In some embodiments, the first set of reaction conditions comprises a temperature in the range of about 60 캜 to about 200 캜 and a pressure in the range of about 200 psig to about 2000 psig. In some embodiments, the second set of reaction conditions comprise a temperature in the range of about 80 캜 to about 200 캜 and a pressure in the range of about 500 psig to about 2000 psig.

Catalysts suitable for hydrogenation reactions (reduction catalysts) are specific supported heterogeneous catalysts comprising Pt. In all embodiments of the present invention, the catalyst comprises Pt (0) alone or in combination with other metals and / or alloys, at least on the outer surface of the support (i.e., the surface exposed to the reaction components) Lt; / RTI > According to a particular embodiment of the present invention, the catalyst used in the processes comprises Pt and at least one metal (M2) selected from the group of Mo, La, Sm, Y, W, and Re. In various embodiments of the present invention, one or more other d-block metals, one or more rare earth metals (e.g., lanthanide), and / or one or more parent metals (e.g., Al) ≪ / RTI > Typically, the total weight of the metal (s) is from about 0.1% to about 10% or from 0.2% to 10% or from about 0.2% to about 8% or from about 0.2% to about 5% of the total weight of the catalyst. In another preferred embodiment, the total weight of metal of the catalyst is less than about 4%.

The molar ratio of Pt (M1) to (M2) may vary, for example, from about 20: 1 to about 1:10. In various preferred embodiments, the M1: M2 molar ratio is in the range of about 10: 1 to about 1: 5. In another preferred embodiment, the ratio of M1: M2 is in the range of about 8: 1 to about 1: 2.

According to the present invention, the preferred catalyst is a supported, heterogeneous catalyst, wherein the catalyst is on the surface of the support. Suitable supports include, for example, acidic ion-exchange resins, gamma alumina, alumina fluoride, sulfate or tungsten accelerated zirconia, titania, silica, silica-promoted alumina, aluminum phosphate, tungsten oxide supported on silica- Acidic clays, supported inorganic acids, and zeolites. The support material can be prepared using methods known in the art such as thermal treatment, acid treatment, or by the introduction of dopants (e.g., metal-doped titania, metal-doped zirconia (e.g., tungstated zirconia ), Metal-doped ceria, and metal-denatured niobia). Preferred supports include zirconia, silica and zeolite. When a catalyst support is used, the metal may be adhered using procedures known in the art including, but not limited to, initial wetting, ion-exchange, adhesion-deposition, and vacuum impregnation. When two or more metals are attached to the same support, they may be attached sequentially or simultaneously. In various embodiments, the catalyst after the metal deposition is dried at a temperature ranging from about 20 [deg.] C to about 120 [deg.] C for a time period ranging from at least about 1 hour to about 24 hours. In these and other embodiments, the catalyst is dried under sub-atmospheric conditions. In various embodiments, the catalyst is reduced and then dried (e. G., Time period, for example, flowing a 5% H ₂ in N ₂ at a temperature of at least about 200 ℃ for at least about 3 hours, by). Also in these and other embodiments, the catalyst is calcined in air at a temperature of at least about 200 DEG C for a time period of at least about 3 hours.

The hydrogenation reaction (s) can also be carried out in the presence of a solvent for the furfural substrate. Suitable solvents for use in conjunction with hydrogenation reactions to convert furfural to a reaction product comprising a diol or triol can include, for example, water, alcohols, esters, ethers, ketones, or mixtures thereof. In various embodiments, the preferred solvent is water.

Generally, the hydrogenation reaction can be carried out in a batch, semi-batch or continuous reactor design using a fixed bed reactor, a trickle bed reactor, a slurry bed reactor, a mobile bed reactor, or any other design that allows heterogeneous catalysis. Examples of reactors can be found in Chemical Process Equipment Selection and Design, Couper et al., Elsevier 1990, incorporated herein by reference. It should be understood that furfural substrates (e.g., 5- (hydroxymethyl) furfural), hydrogen, certain solvents, and catalysts may be introduced into suitable reactors, individually or in various combinations.

The chemical catalytic conversion of the furfural substrate to the 1,6-hexanediol can yield a mixture of products as two separate chemical catalyst reduction steps or as a combined chemical catalytic reduction step. For example, when the furfural substrate is 5- (hydroxymethyl) furfural, the reaction product mixture comprises 1,6-hexanediol and / or 1,2,6-hexanetriol as well as smaller amounts of 1, 5-hexanediol; 1,2,5-hexanetriol; 1,2,5,6-hexane quatrol; 1-hexanol; And 2-hexanol. The production of 1,6-hexanethiol from a furfural substrate (for example, 5- (hydroxymethyl) furfural) is surprisingly very easy. In some embodiments, at least 50%, at least 60%, or at least 70% of the product mixture is 1,2,6-hexanetriol. In some embodiments, the production of HDO is at least about 40%, at least about 50%, or at least about 60%.

The product mixture may be separated into one or more products by any suitable method known in the art. In some embodiments, the product mixture can be separated by fractional distillation at sub-atmospheric pressure. For example, in some embodiments, 1,6-hexanediol can be separated from the product mixture at a temperature of about 90 ° C to about 110 ° C, 1,2,6-hexanetriol can be separated from the product mixture at about 150 ° C to 175 ° C And 1,2-hexanediol and hexanol can be separated from the product mixture at a temperature of about 100 < 0 > C to 125 < 0 > C. In certain embodiments, 1,2,6-hexanetriol can be isolated from the product mixture and recycled to further reduction reactions to produce additional 1,6-hexanediol. The 1,6-hexanediol can be recovered from any other product of the reaction mixture by one or more conventional methods known in the art including, for example, solvent extraction, crystallization or evaporation.

According to the present invention, the production of HDO from the substrate of formula I can be carried out at reaction temperatures ranging from about 60 캜 to about 200 캜, more typically from about 80 캜 to about 200 캜. In various preferred embodiments, the step of converting furfural to 1,2,6-hexanetriol is carried out at a reaction temperature ranging from about 100 ° C to about 140 ° C, and the conversion of 1,2,6-hexanetriol to 1, Conversion to 6-hexanediol is carried out at reaction temperatures ranging from about 120 < 0 > C to about 180 < 0 > C. According to the present invention, the production of HDO from a substrate of Formula I can be carried out at a hydrogen pressure in the range of about 200 psig to about 2000 psig. In various preferred embodiments, the step of converting furfural to 1,2,6-hexanetriol is carried out at a hydrogen pressure in the range of about 200 psig to about 1000 psig, and the conversion of 1,2,6-hexanetriol to 1, The conversion to 6-hexanediol is carried out at a hydrogen pressure in the range of about 200 psig to about 2000 psig.

II. Preparation of hexamethylenediamine from 1,6-hexanediol

The preparation of hexamethylenediamine from 1,6-hexanediol can be carried out using processes known in the art. See, for example, U.S. Pat. 2,754,330; No. 3,215,742; No. 3,268,588; And No. 3,270,059. ≪ / RTI >

In introducing elements of the present invention or its preferred embodiment (s) thereof, the articles "a" and "an" are intended to be singular unless the context allows otherwise, and "the" and " Is intended to mean that there are one or more of the elements. It is to be understood that the terms " comprises, "" including" and "having" are intended to be inclusive and that the use of such terms may include additional elements other than those listed.

Several objects of the invention are achieved from the above viewpoint, and other beneficial results are obtained.

It is intended that all matter contained in the above description should be interpreted as illustrative and not in a limiting sense, since various changes may be made in the composition and process without departing from the scope of the invention.

While the invention has been described in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims.

Example

The following non-limiting examples are provided to further illustrate the present invention.

The reactions were carried out in 1 mL glass vials housed in a pressure vessel according to the procedure described in the examples below. Conversion rate, product yield and selectivity were determined using ion chromatography with an electrochemical detector.

Example  One: Hydroxymethylfurfural  1,6- Hexanediol  transform

A sample of silica Cariact Q-10 (Fuji Silysia) support was dried at 60 占 폚. (NH ₄ ) ₆ Mo ₇ O ₂₄ was added to about 10 mg of solid and stirred to impregnate the support. The solid was calcined at 600 < 0 > C in air for 3 hours. Then, a moderately concentrated aqueous solution of Pt (NO ₃ ) ₂ was added to about 10 mg of solid and stirred to impregnate the support. The sample was dried in an oven at 60 < 0 > C overnight under dry air purge. Next, and it reduced at 350 ℃ under 5 ℃ / min for 3 hours to form a gas at a temperature rising rate of (5% H ₂ and 95% N ₂₎ atmosphere. The final catalyst consisted of about 3.9 wt% Pt and 1.3 wt% Mo.

These catalysts were tested for hydroxymethyl furfural reduction using the following catalyst test protocol. The catalyst (about 8 mg) was weighed into a glass vial insert and an aqueous hydroxymethyl furfural solution (200 μL of 0.1 M) was added. The glass vial insert was loaded into the reactor and the reactor was closed. The atmosphere of the reactor was replaced with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 DEG C and held at each temperature for 300 minutes while shaking the vial. After 300 minutes, the shaking was stopped and the reactor was cooled to 40 占 폚. Then, the pressure in the reactor was gradually released. The glass vial insert was taken out of the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with a flame ionization detector. The results are reported in Table 1.

number metal Support HMF
Conversion Rate (%) 1,2,6-HT
yield(%) BHMTHF
yield(%) 1.6-hexanediol yield (%),
(% Selectivity) 1.2, 6-hexanetriol yield (%),
(% Selectivity) One Pt-Mo Silica Cariact 87 12 One 14 (16) 48 (50)

Example  2: Hydroxymethylfurfural  1,2,6- Hexanetriol  transform

A sample of the alumina support was dried at 120 < 0 > C. A moderately concentrated aqueous solution of Pt (NO ₃ ) ₂ was added to about 8 mg of solid and stirred to impregnate the support. The solids were dried at 120 < 0 > C in air for 16 hours. A moderately concentrated aqueous solution of (NH ₄ ) ₆ Mo ₇ O ₂₄ or La (NO ₃ ) ₃ or Sm (NO ₃ ) ₂ was then added to about 8 mg of solid and stirred to impregnate the support. The sample was dried in an oven overnight at 120 < 0 > C under air. Then, the mixture was calcined at 500 DEG C under air at a temperature rising rate of 30 DEG C / min for 3 hours. The final catalyst consisted of about 4 wt% Pt and various M2 loading (see Table 2).

These catalysts were tested for hydroxymethyl furfural reduction using the following catalyst test protocol. The catalyst (about 8 mg) was weighed into a glass vial insert and an aqueous hydroxymethyl furfural solution (200 μL of 0.4 M) was added. The glass vial insert was loaded into the reactor and the reactor was closed. The atmosphere in the reactor was replaced with hydrogen and pressurized to 200 psig at room temperature. The reactor was heated to 120 DEG C and held at each temperature for 300 minutes while shaking the vial. After 300 minutes, the shaking was stopped and the reactor was cooled to 40 占 폚. Then, the pressure in the reactor was gradually released. The glass vial insert was taken out of the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with a flame ionization detector. The results are reported in Table 2.

number metal M2: Pt mol: mol Support Support
producer HMF
Conversion Rate (%) 1.2, 6-HT yield (%), (selectivity%) One Pt-Mo 0.5 Catalox alumina SBa-200 Sasol 100 48 (50) 2 Pt-Mo 0.25 Alumina AL 2100 Davicat Grace Davison 100 50 (51) 3 Pt-La One Catalox alumina SBa-90 Sasol 100 51 (50) 4 Pt-Sm One Catalox alumina SBa-90 Sasol 100 51 (50)

Example  3: 1,2,6- Hexanetriol  1,6- Hexanediol  transform

Samples of zirconia SZ 61143 (Saint-Gobain Norpro) support were calcined at 750-800 ° C in air for 0.5-2 hours. A moderately concentrated aqueous solution of Pt (NO ₃ ) ₂ was added to about 10 mg of solid and stirred to impregnate the support. The sample was dried in an oven at 60 < 0 > C overnight under dry air purge. Next, and it reduced at 350 ℃ under 5 ℃ / min for 3 hours to form a gas at a temperature rising rate of (5% H ₂ and 95% N ₂₎ atmosphere. The final catalyst consisted of about 3.9 wt% Pt.

These catalysts were tested for 1,2,6-hexanetriol reduction using the following catalyst test protocol. The catalyst (about 10 mg) was weighed into a glass vial insert and 1,2,6-hexanetriol aqueous solution (200 μL of 0.2 M) was added. The glass vial insert was loaded into the reactor and the reactor was closed. The atmosphere of the reactor was replaced with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 DEG C and held at each temperature for 150 minutes while shaking the vial. After 150 minutes, the shaking was stopped and the reactor was cooled to 40 占 폚. Then, the pressure in the reactor was gradually released. The glass vial insert was taken out of the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with a flame ionization detector. The results are reported in Table 3.

number metal Support Support treatment Conversion of 1,2,6-hexanetriol (%) 1.6-hexanediol yield (%),
(% Selectivity) One Pt Zirconia
SZ 61143 750 ° C / 2 hours 91 61 (68) 2 Pt Zirconia
SZ 61143 800 DEG C / 0.5 hour 95 59 (63) 3 Pt Zirconia
SZ 61143 750 ° C / 1 hour 95 58 (62)

Example  4: 1,2,5- Hexanetriol  1,6- Hexanediol  transform

A sample of silica Cariact Q-10 (Fuji Silysia) support was dried at 60 占 폚. (NH ₄ ) ₆ Mo ₇ O ₂₄ or (NH ₄ ) ₁₀ W ₁₂ O ₄₁ was added to about 10 mg of solid and stirred to impregnate the support. The solid was calcined at 600 < 0 > C in air for 3 hours. Then, a moderately concentrated aqueous solution of Pt (NO ₃ ) ₂ was added to about 10 mg of solid and stirred to impregnate the support. The sample was dried in an oven at 60 < 0 > C overnight under dry air purge. Next, and it reduced at 350 ℃ under 5 ℃ / min for 3 hours to form a gas at a temperature rising rate of (5% H ₂ and 95% N ₂₎ atmosphere. The final catalyst consisted of about 3.9wt% Pt and 0.8wt% Mo or 3.9wt% Pt and 1.3wt% W.

These catalysts were tested for 1,2,6-hexanetriol reduction using the following catalyst test protocol. The catalyst (about 10 mg) was weighed into a glass vial insert and 1,2,6-hexanetriol aqueous solution (200 μL of 0.2 M) was added. The glass vial insert was loaded into the reactor and the reactor was closed. The atmosphere of the reactor was replaced with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 DEG C and held at each temperature for 150 minutes while shaking the vial. After 150 minutes, the shaking was stopped and the reactor was cooled to 40 占 폚. Then, the pressure in the reactor was gradually released. The glass vial insert was taken out of the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with a flame ionization detector. The results are reported in Table 4.

number metal Support 1,2,6-hexanetriol
Conversion Rate (%) 1.6-hexanediol
yield(%),
(% Selectivity) One Pt-Mo Silica
Cariact Q-10 78 55 (69) 2 Pt-W Silica
Cariact Q-10 36 33 (92)

Example  5: 1,2,6- Hexanetriol  1,6- Hexanediol  transform

A moderately concentrated aqueous solution of Pt (NO ₃ ) ₂ and (NH ₄ ) ₆ Mo ₇ O ₂₄ was added to about 10 mg of each solid and stirred to impregnate the support. The sample was dried in an oven at 60 < 0 > C overnight under dry air purge. The dried sample was then reduced at 500 ° C or 350 ° C under a forming gas (5% H ₂ and 95% N ₂ ) atmosphere at a temperature ramp rate of 5 ° C / min for 3 hours. The final catalyst consisted of about 3.9 wt% Pt and 0.2 wt% Mo.

These catalysts were tested for 1,2,6-hexanetriol reduction using the following catalyst test protocol. The catalyst (about 10 mg) was weighed into a glass vial insert and 1,2,6-hexanetriol aqueous solution (200 μL of 0.2 M) was added. The glass vial insert was loaded into the reactor and the reactor was closed. The atmosphere of the reactor was replaced with hydrogen and pressurized to 830 or 670 psig at room temperature. The reactor was heated to 160 占 폚. This temperature was maintained for 5 hours with shaking the vial. After 5 hours, the shaking was stopped and the reactor was cooled to 40 占 폚. Then, the pressure in the reactor was gradually released. The glass vial insert was taken out of the reactor and centrifuged. The clear solution was diluted with deionized water and analyzed by gas chromatography with an electrochemical detector. The results are reported in Table 5 below.

number metal Support producer 1,2,6-hexanetriol
Conversion Rate (%) 1.6-hexanediol
yield(%) One Pt-Mo Silica Cariact G-10 Fuji Silysia 54 42

Example  6: 1,2,6- Hexanetriol  1,6- Hexanediol  transform

A sample of the Zeolyst support was dried at 60 占 폚. (NH ₄ ) ₁₀ W ₁₂ O ₄₁ was added to about 10 mg of solid and stirred to impregnate the support. The solid was calcined at 500 < 0 > C in air for 3 hours. Then, a moderately concentrated aqueous solution of Pt (NO ₃ ) ₂ was added to about 10 mg of solid and stirred to impregnate the support. The sample was dried in an oven at 60 < 0 > C overnight under dry air purge. Next, and it reduced at 350 ℃ under 5 ℃ / min for 3 hours to form a gas at a temperature rising rate of (5% H ₂ and 95% N ₂₎ atmosphere.

These catalysts were tested for 1,2,6-hexanetriol reduction using the following catalyst test protocol. The catalyst (about 10 mg) was weighed into a glass vial insert and 1,2,6-hexanetriol aqueous solution (200 μL of 0.2 M) was added. The glass vial insert was loaded into the reactor and the reactor was closed. The atmosphere of the reactor was replaced with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 DEG C and held at each temperature for 150 minutes while shaking the vial. After 150 minutes, the shaking was stopped and the reactor was cooled to 40 占 폚. Then, the pressure in the reactor was gradually released. The glass vial insert was taken out of the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with a flame ionization detector. The results are reported in Table 6 below.

number metal M2: Pt mol: mol Support Conversion of 1,2,6-hexanetriol (%) 1.6-hexanediol yield (%), (selectivity%) One Pt-W 0.33 Zeolite
CBV 720 (Y) 89 49 (60) 2 Pt-W 0.33 Zeolite CP811C-300 (beta) 100 65 (65)

Claims (48)

Converting the carbohydrate source to a furfural substrate;
Reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6-hexanediol; And
Converting at least a portion of the 1,6-hexanediol into hexamethylenediamine
≪ / RTI > wherein the hexamethylenediamine is from a carbohydrate source. Converting the carbohydrate source to a furfural substrate;
Reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce a reaction product comprising 1,2,6-hexanetriol;
Converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol; And
Converting at least a portion of the 1,6-hexanediol into hexamethylenediamine
≪ / RTI > wherein the hexamethylenediamine is from a carbohydrate source. The method of claim 1, wherein the heterogeneous reduction catalyst comprises Pt. 4. The method according to claim 2 or 3, wherein the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re. 5. The process according to any one of claims 2 to 4, wherein the step of converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol is carried out in the presence of a hydrogenation catalyst comprising hydrogen and Pt ≪ / RTI > 6. Process according to any one of claims 2 to 5, characterized in that the yield of 1,6-hexanediol is at least about 40%. 6. Process according to any one of claims 2 to 5, characterized in that the yield of 1,6-hexanediol is at least about 50%. 7. A process according to any one of claims 2 to 6, wherein the yield of 1,6-hexanediol is at least about 60%. 9. The process of any one of claims 1 to 8, wherein the reaction of the furfural substrate with hydrogen is performed at a temperature ranging from about 60 DEG C to about 200 DEG C and a hydrogen pressure ranging from about 200 psig to about 2000 psig How to. 10. A process according to any one of claims 1 to 9, characterized in that the furfural substrate is 5-hydroxymethyl furfural. 11. A method according to any one of claims 1 to 10, wherein the carbohydrate source is a mixture comprising glucose, fructose, or glucose and fructose. 12. A process according to any one of claims 2 to 11, characterized in that the catalyst further comprises a support selected from the group consisting of zirconia, silica, and zeolite. 13. The method of any one of claims 1 to 12, wherein the reaction of the furfural substrate with hydrogen is performed at a temperature in the range of from about 100 DEG C to about 180 DEG C and at a hydrogen pressure in the range of from about 200 psig to about 2000 psig How to. 14. A process according to claim 2, 5 or 13, characterized in that the hydrogenation catalyst comprises Pt and W supported on zirconia. A hexamethylenediamine produced by the process of any one of claims 1 to 14. Converting the carbohydrate source to a furfural substrate; And
Reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol
Hexanediol from a carbohydrate source. ≪ RTI ID = 0.0 > 18. < / RTI > Converting the carbohydrate source to a furfural substrate;
Reacting at least a portion of the furfural substrate with hydrogen in the presence of a Pt containing heterogeneous reduction catalyst to produce a reaction product comprising 1,2,6-hexanetriol; And
Converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol
Hexanediol from a carbohydrate source. ≪ RTI ID = 0.0 > 18. < / RTI > 18. The method of claim 16 or 17, wherein the heterogeneous catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re. 17. The process of claim 16, wherein the step of converting at least a portion of 1,2,6-hexanetriol to 1,6-hexanediol is carried out in the presence of a hydrogenation catalyst comprising hydrogen and Pt. 20. Process according to any one of claims 16 to 19, characterized in that the hydrogenation catalyst is a supported heterogeneous catalyst. 21. Process according to any one of claims 16 to 20, characterized in that the yield of 1,6-hexanediol from the furfural substrate is at least 40%. 21. Process according to any one of claims 16 to 20, characterized in that the yield of 1,6-hexanediol from the furfural substrate is at least 50%. 21. Process according to any one of claims 16 to 20, characterized in that the yield of 1,6-hexanediol from the furfural substrate is at least 60%. 22. The process of any one of claims 16 to 21, wherein the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of from about 60 DEG C to about 200 DEG C and at a hydrogen pressure in the range of from about 200 psig to about 2000 psig How to. 25. The method according to any one of claims 16 to 24, wherein the furfural substrate is 5-hydroxymethyl furfural. 26. The method according to any one of claims 16 to 25, wherein the carbohydrate source is a mixture comprising glucose, fructose, or glucose and fructose. 27. The process according to any one of claims 16 to 26, wherein the catalyst further comprises a support selected from the group consisting of zirconia, silica, and zeolite. 28. The process of any one of claims 16-27, wherein the reaction of the furfural substrate with hydrogen to produce 1,2,6-hexanetriol is carried out at a temperature ranging from about 100 < 0 > C to about 140 & RTI ID = 0.0 > 1000 psig. ≪ / RTI > 29. A process according to any one of claims 16 to 28, characterized in that the catalyst comprises Pt and W supported on zirconia. 29. A 1,6-hexanediol produced by the process of any one of claims 16 to 29. (a) converting a carbohydrate source to a furfural substrate;
(b) reacting hydrogen with at least a portion of the furfural substrate with a reaction product comprising 1,2,6-hexanetriol in the presence of a heterogeneous reduction catalyst comprising Pt;
(c) reacting at least a portion of 1,2,6-hexanetriol with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol; And
(d) converting at least a portion of the 1,6-hexanediol to hexamethylenediamine
, Wherein steps b) and c) are performed in a single reactor, wherein the hexamethylenediamine is prepared from a carbohydrate source. (a) converting a carbohydrate source to a furfural substrate;
(b) reacting hydrogen with at least a portion of the furfural substrate with a reaction product comprising 1,2,6-hexanetriol in the presence of a heterogeneous reduction catalyst comprising Pt; And
(c) reacting at least a portion of 1,2,6-hexanetriol with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol
, Wherein steps b) and c) are performed in a single reactor. The method of claim 31 or 32, wherein the heterogeneous reduction catalyst further comprises W. 34. The method of any one of claims 31 to 33, wherein steps (b) and (c) are performed at a temperature in the range of about 60 DEG C to about 200 DEG C and a hydrogen pressure in the range of about 200 psig to about 2000 psig Lt; / RTI > 35. A process according to any one of claims 31 to 34, characterized in that the Pt-containing catalyst of step b) and c) is different and the temperature and pressure at which steps b) and c) are carried out are substantially equal. 35. A process according to any one of claims 31 to 34, characterized in that the temperature and pressure at which steps b) and c) are carried out are different. 32. The method of claim 31 or 32 wherein step b) is performed at a temperature in the range of from about 100 DEG C to about 140 DEG C and a pressure in the range of from about 200 psig to about 1000 psig, and step c) And a pressure in the range of about 200 psig to about 2000 psig. 37. The method of any one of claims 31-37, wherein the yield of 1,6-hexanediol from the furfural substrate is at least about 40%. 37. The method of any one of claims 31-37, wherein the yield of 1,6-hexanediol from the furfural substrate is at least about 50%. 37. The process of any one of claims 31-37, wherein the yield of 1,6-hexanediol from the furfural substrate is at least about 60%. 41. The method of any one of claims 31-40, wherein the carbohydrate source is a mixture comprising glucose, fructose, or glucose and fructose. 42. The process according to any one of claims 31 to 41, wherein steps (b) and (c) are carried out in one reaction zone. 43. A process according to any one of claims 31 to 42, characterized in that the catalyst comprises Pt and W supported on zirconia. A hexamethylenediamine produced by the process of any one of claims 31 and 33 to 43. A 1,6-hexanediol produced by the process of any one of claims 32 and 33 to 43. Converting the carbohydrate source to a furfural substrate; And reacting hydrogen with at least a portion of the furfural substrate in the presence of a heterogeneous reduction catalyst comprising Pt to produce a compound of formula II.

Wherein X ² and X ³ are each selected from the group of hydrogen and hydroxyl. 47. The method of claim 46, wherein the catalyst further comprises W. 47. The method of claim 46, wherein the catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re.